C11 alcohols and corresponding acetic acid esters



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and 3,140,311 CH3 CH3 C11 ALcoHoLs AND coRREsPoNDrNG \C/ 1g ACETIC ACID ESTERS H/ Willard T. Somerville, Fair Haven, NJ., assignor to Inter- HC C national Flavors & Fragrances Inc., New York, N.Y., H H a corporation of New York i 2 Filed Mar. 3, 1961, Ser. No. 93,138 C C s claims. (c1. 26o-48s) H2 H2 4(4-methyLS-pentenyl) 5,6 dihydro-2H-pyran This invention relates to products of formaldehyde and These isomers may be present singly, mas a mixture myrcehe and Processes for making same Prodllcts made Hereinafter these isomers are sometimes referred to, for in accordance with my invention are useful as perfumes. brevity, as methyl pentenyl dihydropyran. I have also Myrcetle has heretofore been heated With trioXymethylfound that the production of this methyl pentenyl dihyene, with an acid catalyst to form resins, in accordance dropyran is accompanied by the production of acyclic with the patent t0 Rnlnnlelsburg NO- 2,397,205 These 15 primary C11 alcohols and their corresponding acid esters. resins are stated to be useful in textile finishes. I have also found in accordance with my invention In Webb Patent 2,919,290, Such Production of resin by that I can produce these compounds by a process which reaction of myrcene with formaldehyde and a catalyst is comprises heating a mixture of myrcene, formaldehyde recognized In coll, commencing line 35 of the Webb and a mild acid in proportions sutlcient to react only 1 patent the following statement is made: 20 mol of formaldehyde with 1 mol of myrcene. The form- These tWo acyclic triehes (referring to myrcene and aldehyde is used in the form of paraformaldehyde. Aqueallo-ocimene) react With formaldehyde, but their high ous formaldehyde or a substance producing formaldedegree of unsaturation makes them particularly susceptible hyde n ndeithe reaction conditions herein may also be to polymerization on thermal or acid treatments such as used, The mild acid may be formic, acetic, trimethyl those necessary to provoke reaction of formaldehyde and acetic or propionic acid, or equivalent. The esters formed ierPerie- Therefore it is not Satisfactory to Utilize such by these acids accordingly include the formate, acetate, terpenes for reaction with formaldehyde to produce acyclic propionate and trimethyi aeetates, alcohols of eleven carbon atoms. The mixture of myrcene, formaldehyde and acid is Webb accordingly Proposed to hydrogenate myrcene, heated and reuxed for several hours. The product is and then to react hydrogenated myrcene with formaldethen washed with water and a mild alkali, and the rehyde- By hydrogenating myrcene before treatment With sulting oil is separated and distilled to recover unreacted formaldehyde he avoided resin formation. myrcene, and thereafter from the remainder is distilled The Principal oblect of the Present invention, accordand recovered the unpolymerized reaction products above ingly, is to produce a series 0f useful unpolymerized Iementioned. There is also distilled and recovered a mixaction Products of myrcehe and formaldehyde, and to ture of C11 acyclic primary alcohols and mild acid esters provide a simple, efficient process for producing Such HI1- thereof, which are subsequently separated from each other. polymerized products. Y The reaction occurring is as follows:

The invention comprises the novel products, the speci- Amie acid iic embodiments of which are described hereinafter by CmHia -l- (CHBO)x CnHno way of example, and in accordance with which I now Myrceue Heat Methyl prefer to practice the invention. formaldehyde pentenyi I have found in accordance with my invention that I dihydmpymn can produce from myrcene, formaldehyde and a mild 0105150122033 *l* CwHnCHOCCH acid one or more compounds having the formula: [l

CH3 CH3 45 Primary acyclic Primary acyclic H, Y Cnalcohol acetate C H/ The exact amount of acids, such as glacial acetic acid, HC (li Iii and formaldehyde used to react with a iixed amount of mi; R, myrcene can be varied to some extent. Since a certain \C/ \C/ amount of higher boiling products and residue is formed H2 H2 in the reaction, the yield of desired products can be varied by varying the amount of acid and formaldehyde, and also the time of heating.

In this reaction it is customary to add a small amount of a preservative. The object of adding a preservative is to prevent the polymerization of the myrcene. The use where one of the symbols R and R is oxygen and the other is CH2. i

In other words, the formula given is for two isomers in which the -O- is at different positions on the ring at the right as follows: i of the preservative is not at all essential to the reaction,

CH3 CH3 but is of some help. I commonly use lonol, the com- H2 mercial name for a preservative. It is 2,6 di-tertiary butyl H/ para cresol. Other preservatives inert to formaldehyde HCI) (n) (im may be used, namely Antioxidant 702, 4,4 methylene H2O C O bis (2,6 di-tertiary butyl phenol), 2,2 methylene bis (4 \C/ \C/ methyl 6 tertiary butyl phenol), 4,4' bis (2,6 di-tertiary H2 H2 butyl phenol), and 4,4 methylene bis (6 tertiary butyl 3(4-methy1-3-penteny1) 5,6 dihydro-ZH-pyran 65 Ortho Cresoi), AiitioXidar1t720- The following are examples of the manner in which I now prefer to practice the invention. The examples are illustrative and the invention is not to be considered as restricted thereto except as indicated in the appended claims.

Example l .-A mixture of 4080 grams of myrcene 93% (28 mols), 600 grams paraformaldehyde 91% flake (18 mols) and 1600 grams of glacial acetic acid (26 mols) are refluxed for l hours at atmospheric pressure. The liquid temperature is 107 to 109 C. At the end of this reux period the material is cooled to room temperature and then poured into an equal volume of water, and washed three times with hot water and once with sodium bicarbonate solution. The separated oil was distilled over a 14 protruded packed column to a liquid temperature of 100 C., using a vacuum of 25 mm. of mercury to recover the myrcene. The remainder of the material was distilled without a column at a vacuum of 2 to 3 mm. One half percent Ionol was added before this distillation was started, as a preservative. 1,736 grams of myrcene were recovered from the first distillation, and an additional 4-46 grams from the distillation without a column. A fraction of the desired material boiling between 68 C. and 148 C. at 3 to 5 mm. amounted to 1,237 grams. Higher boiling material amounted to 422 grams, and the residue was 317 grams.

The 1,237 grams of product, when redistilled using a fractionating column, yielded 510 grams of methyl pentenyl dihydropyran.

The pure methyl pentenyl dihydropyran separated from the reaction mixture by fractionation had the following physical constants:

B.P. 60-2/3.5 mm.; 53-54/1.9 mm.

It analyzes as C=79.l5%, H=10.75%. Calculated for CuHlgO:

Gas chromatography on this substance, even on a capillary column, shows only one peak, and thus fails to establish the presence of more than one constituent.

A nuclear magnetic resonance chart (said term nuclear magnetic resonance being hereinafter sometimes referred to as NMR) is included as part of this application, and is referred to below. The nuclear magnetic resonance band for the hydrogens in the O-CHZ- C=C group (chemical shift Tau=5.86) shown on the magnetic resonance chart is presumed to be due to an unresolved trio of peaks, resulting from a mixture of 4(4-methyl-3- pentenyl) 5,6-2H-pyran which would give a doublet, and 3(4-methyl-3-pentenyl) 5,6 dihydro-2H-pyran, which would give a singlet. Determination of nuclear magnetic resonance was made in accordance with the disclosure thereof contained in Applications of Nuclear Magnetic Resonance Spectroscopy, by L. M. Jackman, Pergamon Press, New York, 1959.

In addition, an alcohol-ester section of 404 grams B.P. 73-100" C./0.7-0.8 mm., 111320 of 1.4840-1.4950 was obtained. This fraction has a HD2 of 1.4908, ya D1520 0.9300, and when saponied with Normal sodium hydroxide solution required 1.8() rnl. After acetylation with acetic anhydride, one gram of acetylated product required 5.50 ml. of Normal sodium hydroxide for saponication. The infrared spectrum, a drawing of which is referred to below, shows both the presence of alcohol and ester groups. This spectrum represents the mixture obtained by this example. It will vary somewhat depending on the exact composition of the mixture produced. The alcohol in the above alcohol-ester section was recovered as set forth in Example 7 below. The acetate was prepared from this alcohol in accordance with Example 8 below. The properties of both the alcohol and ester are given in said examples.

I have also found that other organic acids, besides acetic acid, can be used in this reaction. The following is an example using propionic acid:

Example 2.-3060 grams of myrcene, 93% purity, 900 grams of paraformaldehyde 91%, and 2960 grams of propionic acid (99% pure) were refluxed together for l0 hours. The liquid temperature was approximately 112 C. When the reflux time was over, the mixture was poured into water and the separated oil was washed several times with water and then with warm sodium bicarbonate solution until free of acid.

The unreacted myrcene was recovered by distillation at 25 mm. of vacuum to a liquid temperature of 100 C. 1306 grams myrcene were recovered. The remainder was distilled at 1 mm. to separate residue (178 grams). In this way, 1542 grams of crude product was obtained, and which was redistilled through a l5" protruded packed column at 1 mm. to yield:

692 grams methyl pentenyl dihydropyran fraction-BR 63-68/ 1 mm. 287 grams primary acyclic C11 alcohol-propionate fraction-B.P. 83-12l/1 mm. 374 grams higher boiling material-BP. 127-143 1 mm.

88 grams residue. Example 3.-Reaction of myrcene with formaldehyde in the presence of formic acid:

Ina flask, fitted with a stirrer, thermometer, reflux condensers, and heating mantle, was placed:

3060 grams of myrcene (97% pure) 2000 grams of 90% formic acid 900 grams of paraformaldehyde 91% flake 30 grams of Ionol.

The mixture was reuxed for 10 hours. The liquid temperature varied between and 115 C. It was then cooled and poured into water and the separated oil washed twice with hot water and once with sodium bicarbonate solution. The material was distilled from a flask without a column in an attempt to recover myrcene, as there was very little unreacted myrcene. The material was then distilled in a vacuum of 2 to 3 mm. to yield the following fractions:

B. P. 28 to 53 C., 118 grams B.P. 53 to 67 C., 225 grams B.P. 71 to 115 C., 1026 grams (C11 primary acyclc alcohol-ester section) B.P. to 131 C., 513 grams (higher boiling material) Residue, 217 grams.

The alcohol-ester section mentioned above contains 62% ester when analyzed by saponification, assuming a molecular weight of 194 for the formate. It analyzed 34.1% free alcohol by acetylation and correcting for the known ester content. The specific gravity at 20/20 was 0.9890; the index of refraction at 20 was 1.4909.

The 225 gram section, mentioned above, was carefully refractionated to obtain methyl pentenyl dihydropyran. Upon refractionation 58 grams of crude methyl pentenyl dihydropyran were obtained. This crude material was found to contain 30% of methyl pentenyl dihydropyran, by vapor phase chromatography.

Results of this experiment indicate that the reaction of myrcene and paraformaldehyde in the presence of formic acid is much more vigorous and more complete than the other acids. Very little or no myrcene is recovered unreacted. Also, the amount of methyl pentenyl dihydropyran formed is quite small, while the amount of alcoholester mixture is larger than with acetic acid.

Example 4.-Using beta pinene pyrolyzate containing about 75% of myrcene:

A mixture of- 4080 grams of beta pinene pyrolyzate 900 grams of paraformaldehyde (91%) 2400 grams of glacial acetic acid and 50 grams of Ionol was reacted and worked up as in Example 1 to give corresponding fractions. The following products were obtained:

1543 grams of recovered myrcene 525 grams methyl pentenyl dihydropyran 1053 grams of C11 alcohol and corresponding ester fraction 382 grams higher boiling products, and

414 grams of residue.

The alcohol ester fraction boiled at 70-93 C. at 1.5 mm., and had a D102o of 0.9584 and a refractive index at 20 of 1.4900. Upon saponication it required 1.98 ml. of Normal sodium hydroxide solution per gram of sample.

After acetylation a sample required 5.55 rnl. of Normal sodium hydroxide solution to saponify 1 gram of acetylated product.

Example 5 .--Using pivalic acid (trimethyl acetic acid):

In this example I used-.-

816 grams of myrcene (96%) 1224 grams of trirnethyl acetic acid 240 grams of paraformaldehyde 91%, and grams of Ionol.

The mixture was refluxed for 10 hours, during which time the liquid temperature varied from 115 C. at the beginning to 140 C. at the end of 10 hours. The mixture was decomposed with water and washed with very hot water, and then repeatedly washed with. hot sodium bicarbonate solution until neutral. It was then vacuum distilled to yield the following products:

217 grams of recovered myrcene 56 grams methyl pentenyl dihydropyran 186 grams of C11 alcohols and corresponding ester fractions, B.P. 116 to 142 C. at 0.7 mm., 132020 0.8865. Index of refraction at 20-1.4933.

1 gram of this material required 0.57 ml. of Normal sodium hydroxide solution for saponitication. After acetylation 1 gram of acetylated product required 0.82 rnl. of Normal sodium hydroxide solution for saponication.

153 grams of residue.

Example 6.--Using aqueous formaldehyde:

In this example I react a mixture of 2040 grams of myrcene (91%) 1600 grams of glacial acetic acid, and 4425 grams of formaldehyde, aqueous solution (37%).

This mixture was refluxed and stirred for l0 hours. It was then poured into Water and the oily layer separated and washed with water and sodium bicarbonate solution. The crude oil was then worked up as in Example 1 to yield:

1056 grams of recovered myrcene 23 grams of methyl pentenyl dihydropyran 175 grams of C11 alcohols and corresponding esters, B.P. 62 to 72 C. at 1 mm. Index of refraction at 20- 1.4S69, D202 0.9537

227 grams of higher boiling material, and

379 grams of residue.

The alcohol-ester section when saponied was found to have an ester content equivalent to 0.12 ml. of Normal sodium hydroxide per gram. An examination of this material by infrared indicated that this material consisted principally of alcohols.

Example 7.--Saponiiication of alcohol ester mixture of Example 1:

The C11 acyclic alcohol and corresponding ester section obtained as in Example 1, was saponied by refluxing with 10% ethyl alcoholic sodium hydroxide, followed by recovery of the ethanol, washing neutral, and distilling. In this manner C11 alcohols were obtained which when vacuum distilled boiled at 60 to 96 C. at 0.6 mm. Upon refractionation, an alcohol, B.P. 66 at 0.25 mm. of mercury, index of refraction at 20 1.4912, was obtained. It ultraviolet absorption curve showed a maximum at 224.5 mm., and its extinction coeiicient or epsilon value Was calculated as 17,000 based on a molecular weight of 166. When tested for diene content by the standard Vmaleic anhydride procedure, it showed a diene content of 99%. By gas chromatography this material tested as being 97% pure. Examination of the NMR spectrum of said alcohol, included in the drawings accompanying this application, indicates the following NorE.-Tau values are relative to tetramethyl silane.

In accordance with said examination and examination of the infrared spectrum, also included in the drawings herewith, the formula of the alcohol Was determined t0 be 2-isopropenyl-5-methylene--heptene-l-ol, corresponding to the following structural formula:

Example 8.--The 2-isopropenyl-S-methylene-6-heptene- 1ol prepared as described in Example 7, was acetylated by refluxing with an equal weight of acetic anhydride for three hours. The reaction mixture was then cooled, washed with warm water to destroy the excess acetic anhydride, and then washed further with water until neutral. The crude ester was then dried and vacuum distilled. It boiled at 53 to 54 C. at 0.05 mm. of mercury pressure. It had a density at 20/ 15 of 0.925; index of refraction 121320 1.4737. Its purity was 94.5% when saponied by alcoholic sodium hydroxide and by gas chromatography. Its ultraviolet curves showed a maximum at 22.5 millimicrons, and its extinction coecient or epsilon value at this wave length was 16,570 calculated on the basis of a molecular weight of 208.3. Examination of the NMR spectrum of said alcohol, which establishes the structure of the corresponding acetate, coupled with examination of the infrared spectrum of said acetate, included in the drawings herewith, determines the formula for the acetate to be 2-isopropenyl-5-rnethylene--heptene-l-yl acetate. The structural formula thereof is:

In the accompanying drawings forming part of this specification:

FIG. 1 is an infrared spectrograph of the alcohol produced by my process;

FIG. 2 is a nuclear magnetic resonance chart of the alcohol obtained by my process.

FIG. 3 is an infrared spectrograph of the mixture of C11 alcohols and esters obtained in accordance with Example 1, and

FIG. 4 is an infrared spectrograph of the acetic acid ester of the alcohol obtained by my process.

The methyl pentenyl dihydropyran is a perfume material having a strong refreshing floral odor with rose, muget, violet and limey character. It is useful in a wide range of perfumes from floral to herb-cologne blends. The C11 alcohols are perfume materials having a very rich rose-violet note of distinctive character. The mixture of C11 alcohols and their esters is a perfume material having an odor somewhat reminiscent of the above mentioned alcohols, but drier and more herbaceous. The C11 alcohol designated as Z-isopropenyl-S-methylene-6- heptene-l-ol is a perfume. It has a powerful, persistent, unique and pleasant odor of pronounced violet character. The acetate of the last mentioned alcohol has a natural and individualistic odor. It is also a perfume. It has a pleasant green, plant-like, chrysanthemumand colognelike odor. It is useful as part of the perfumes geranium, neroli and bergamot.

This application is a continuation-in-part of my copending application Serial No. 33,444, filed June 2, 1960, now Patent No. 3,030,384. Matter not herein claimed is claimed in said copending application.

I claim:

1. The mixture of C11 alcohols and corresponding S acetic acid esters having the respective empirical formulae C10H15CH2OH and and having the infrared spectrum shown in FIG. 3, and the following physical constants:

B.P. 73-100 C. at 0.7-0.8 mm.

:11)20 1.4908, and

D1520 0.9300. 2. The compound having the formula:

C153 /CHg /CHZ OH-CH2.HC CH H10 `=CII3 3. The compound having the formula:

Ogg /CHZ C CII; CHE-(IJ-o-CHLHC CH O H2 :CH2

C Hz

Bain Feb. 1, 1944 Webb Dec. 29, 1959 UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent Noa 3Y lLlOVSll July 7,7 1964 WllalfdY T Somerville lt s hereby cert2ed--that err-0E appears in the vabove numbered. patent requiring correction and than:r the said Letters Patent should read es corrected below.

Column 2, line 43M72 the Lfornr'iula fer Primary acyelc acetate should appear as shown below instead of as in J@he patenti:`

CTOHTSCHQGGHD (SEAL) S11-@med and Sealed *cms 10th day of November 1964 Attest:

ERNEST w. swTDEE E l EDWARD Je. :BRENNER Anesting Officer Commissioner .of Ptents 

1. THE MIXTURE OF C11 ALCOHOLS AND CORRESPONDING ACETIC ACIDS ESTERS HAVING THE RESPECTIVE EMPIRICAL FORMULAE C10H15CH2OH AND 